CN101386768A - Cationic electrodeposition paint compositions - Google Patents

Cationic electrodeposition paint compositions Download PDF

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Publication number
CN101386768A
CN101386768A CN200810213834.5A CN200810213834A CN101386768A CN 101386768 A CN101386768 A CN 101386768A CN 200810213834 A CN200810213834 A CN 200810213834A CN 101386768 A CN101386768 A CN 101386768A
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epoxy
quality
resins
paint composition
electric deposition
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CN101386768B (en
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西口滋朗
岛崎昭彦
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
    • C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
    • C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/443—Polyepoxides
    • C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
    • C09D5/4438—Binder based on epoxy/amine adducts, i.e. reaction products of polyepoxides with compounds containing amino groups only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4473—Mixture of polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/90—Compositions for anticorrosive coatings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Molecular Biology (AREA)
  • Paints Or Removers (AREA)

Abstract

This invention discloses cationic electrodeposition paint compositions which comprise specific amino group-containing modified epoxy resin, specific xylene-formaldehyde resin-modified, amino group-containing epoxy resin and blocked polyisocyanate curing agent at specific blend ratios, and which can form coating film of excellent film thickness retention, finished appearance and electrocoatability on galvanized alloy steel sheet and of good corrosion resistance, even when the amount of volatile organic compound in the cationic electrodeposition paint is reduced.

Description

Cation electric deposition paint composition
Technical field
The present invention relates to contain amino modified epoxy (A), xylene formal dehyde resin modification and contain amino Resins, epoxy (B) and block polyisocyanate curing agent (C) cation electrodeposition coating as the water dispersible excellence of resinous principle, even if particularly relate to the volatile organic compounds that reduces in the cation electrodeposition coating, the suitable property of galvanic deposit coating on thickness retention, processibility and the alloy galvanized steel plate is also excellent and can form the good cation electric deposition paint composition of filming of non-corrosibility.
Background technology
Cation electric deposition paint composition is because the coating operability is excellent and formed non-corrosibility of filming is good, and therefore the bottom-coating as the conductive gold metal products such as body of a motor car that require these performances is extensive use of.
The resin that uses in the cation electric deposition paint composition typically uses the organic solvent manufacturing, be engaged in the coating as the resin solution that contains organic solvent (varnish), so the gained cation electric deposition paint composition contains organic solvent.
The cation electric deposition paint composition that contains organic solvent has following technique effect: wetting ability and hydrophobic balance are good, can not reduce the resin water dispersible as the cation electric deposition paint composition constituent, the paint stability excellence; Through the time the thickness retention or the processibility of filming good; The suitable property excellences of galvanic deposit coating on the alloy galvanized steel plate etc. were for example used ethylene glycol monobutyl ether (171 ℃ of boiling points), ethylene glycol mono hexyl ether (208 ℃ of boiling points), propylene glycol list propyl ether (150 ℃ of boiling points), pimelinketone organic solvents such as (145 ℃ of boiling points) in the past in cation electric deposition paint composition.
In recent years, be in the consideration of environment etc., pair volatile organic compounds (hereinafter being called " VOC ") restriction or hazardous property topsoil material restriction (HAPs restriction) are arranged, limit the use of these organic solvents.Organic solvent can be removed from cation electric deposition paint composition by desolventizing, can obtain the coating composition of low VOC thus.But, during the content of the volatile organic compounds (VOC) in reducing cation electric deposition paint composition, can take place through the time thickness retention or the problem that reduces etc. such as the suitable property of galvanic deposit coating on the processibility of filming, alloy galvanized steel plate.
As the motion that is used to address this is that, for example the spy opens and discloses interpolation organic acid and water in the resin that the composition of the diglycidylether of the diglycidylether that comprises more than a kind alcohol by (A) at least and at least a kind of 2 yuan of phenol and (B) at least a kind of 2 yuan of phenol reaction obtain in the clear 63-92637 communique, thereby Oxyranyle is transformed into the electrocoating paint that contains cationic Resins, epoxy of cation radical manufacturing.But, the non-corrosibility deficiency of filming that forms by the electrocoating paint that contains this cationic Resins, epoxy.
In addition, the spy opens the 2003-221547 communique and discloses and contain that to make xylene formal dehyde resin and contain the Resins, epoxy that xylene formal dehyde resin modification that the Resins, epoxy reaction of amino compound and epoxy equivalent (weight) 180～2500 forms contains amino be the cation electrodeposition coating of matrix resin.But, uses separately the xylene formal dehyde resin modification contain amino Resins, epoxy as the cation electrodeposition coating of matrix resin when seeking to hang down VOCization, thickness retention has problem, in addition, because the xylene formal dehyde resin modification contains the water dispersible deficiency of amino Resins, epoxy, therefore in order to ensure water dispersible, be necessary that volume ground adds neutralizing agent, generation problem etc. aspect the suitable property of galvanic deposit coating on processibility and alloy galvanized steel plate.
And then the spy opens flat 8-245750 communique and discloses and contain the Resins, epoxy (A) made by the diglycidylether of the polyether polyol with 350～5000 average epoxy equivalent (weight)s or by the cation electrodeposition coating of the Resins, epoxy (B) of the diglycidylether of the polyether polyol with 300～5000 average epoxy equivalent (weight)s of partially end-blocked (sealing) manufacturing.But, the non-corrosibility deficiency of filming that the cation electrodeposition coating of being put down in writing by above-mentioned communique that contains resin forms.
The spy opens the 2001-3005 communique and has put down in writing polyether polyols such as polyether polyol that contain aromatic nucleus by cooperating alkylene base system polyether polyol such as polymethylene glycol, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol or bis-phenol being reacted separately or make bis-phenol and form with the glycol reaction, can obtain to hang down VOC and make the galvanic deposit coating of film excellence, alloy galvanized steel plate and the coating of non-corrosibility excellence.
In addition, the spy opens the 2006-274234 communique openly by cooperating the special polyether compound of molecular weight below 1000, can obtain volatile organic solvent content few (low VOC) even if galvanic deposit is coated on the electrocoating paint that pin hole, non-corrosibility and paint stability excellence can not take place on the Rustproof Steel Plate yet.
But, when volume in electrocoating paint is added the following special polyether compound of the special polyether polyol of opening the record of 2001-3005 communique or the special molecular weight amount of opening the record of 2006-274234 communique 1000, the non-corrosibility of filming in formation reduces, electrocoating paint when being subjected to mechanical load for a long time, have the problem that paint stability might reduce etc.
Summary of the invention
Even if the object of the present invention is to provide the volatile organic compounds that reduces in the cation electrodeposition coating, the suitable property of galvanic deposit coating on thickness retention or processibility and the alloy galvanized steel plate is also excellent, and can form the good cation electrodeposition coating of filming of non-corrosibility.
The inventor etc. further investigate, the result this time finds by using specific modified epoxy (A) that contains amino and xylene formal dehyde resin modification to contain amino Resins, epoxy (B) and block polyisocyanate curing agent (C), cooperate these materials to make cation electrodeposition coating with specific ratio, can reach above-mentioned purpose, and then finish the present invention.
Therefore, the invention provides a kind of cation electric deposition paint composition, it is characterized in that it contains:
(A) contain amino modified epoxy, its following acquisition: making the di-epoxy compounds (a1) that is selected from di-epoxy compounds (a12) shown in di-epoxy compounds (a11) shown in the general formula (1) and the general formula (2) and epoxy equivalent (weight) is that 170～500 Resins, epoxy (a2) and bisphenol cpd (a3) react and obtain modified epoxy (A1), make gained modified epoxy (A1) and contain amino compound (A2) reaction, thereby obtain;
Figure A200810213834D00061
(in the formula, m or the individual R of n 1Identical or different, represent respectively the alkyl of hydrogen atom or carbonatoms 1～6, m and n be respectively 0 or integer and m+n=1～20)
Figure A200810213834D00062
(in the formula, y R 2Identical or different, represent the alkyl of hydrogen atom or carbonatoms 1～6 respectively, x is 1～9 integer, y is 1～50 integer)
(B) by to make epoxy equivalent (weight) be 180～2500 Resins, epoxy (b1) with have the xylene formal dehyde resin (b2) of phenol hydroxyl and contain the Resins, epoxy that xylene formal dehyde resin modification that amino compound (b3) reaction obtains contains amino; And
(C) block polyisocyanate curing agent,
With mentioned component (A), (B) and solid state component total mass (C) is benchmark, contains 5～60 quality % compositions (A), 5～60 quality % compositions (B) and 10～40 quality % compositions (C).
Cation electric deposition paint composition of the present invention contains the modified epoxy (A) that contains amino of water dispersible excellence as resinous principle, the paint stability excellences such as filterableness of suitable property of the filtration of for example ultrafiltration (UF) film or microfroc filter.
Cation electric deposition paint composition of the present invention since contain specific contain amino modified epoxy (A) and xylene formal dehyde resin modification contain amino Resins, epoxy (B) both as resinous principle, therefore the property excellence is fitted in the galvanic deposit coating on non-corrosibility and the alloy galvanized steel plate, even if reduce the volatile organic compounds in the cation electrodeposition coating, the galvanic deposit of also playing on thickness retention excellence and processibility, the alloy galvanized steel plate is coated with the unusual effect of fitting property and non-corrosibility excellence.
Cation electric deposition paint composition below is described in further detail.
Contain amino modified epoxy (A):
In the cation electric deposition paint composition of the present invention, contain the amino following acquisition of modified epoxy (A) as what one of resinous principle used: di-epoxy compounds (a1) and the epoxy equivalent (weight) that makes the compound (a12) of the compound (a11) that is selected from above-mentioned formula (1) and above-mentioned formula (2) is that 170～500 Resins, epoxy (a2) and bisphenol cpd (a3) react and obtain modified epoxy (A1), make gained modified epoxy (A1) and contain amino compound (A2) reaction, thereby obtain.
Di-epoxy compounds (a1):
Di-epoxy compounds (a11) is the compound shown in the formula (1), for example can followingly make: add the alkylene oxide shown in the accepted way of doing sth (3) on dihydroxyphenyl propane, make the reaction of the polyether compound of gained C-terminal and epihalohydrins carry out diepoxyization and make.
Figure A200810213834D00071
(in the formula, m or the individual R of n 1Identical or different, represent hydrogen atom or carbonatoms 1～6, preferred 1～2 alkyl, particularly R respectively 1Be hydrogen atom and methyl, m and n be respectively 0 or integer, be preferably 1～10 integer and m+n=1～20, be preferably 2～15)
(in the formula, R 1As described in above-mentioned definition)
As the alkylene oxide of above-mentioned formula (3), for example can enumerate carbonatomss 2～8 such as oxyethane, propylene oxide, butylene oxide ring, preferred 2～4 alkylene oxide, wherein optimization ethylene oxide (the R of formula (3) 1Compound for hydrogen atom) and the propylene oxide (R of formula (3) 1Compound for methyl).
In addition, di-epoxy compounds (a12) is the compound shown in the formula (2), for example can followingly make: make aklylene glycol as initiator, make R 1Be replaced as R 2The alkylene oxide ring-opening polymerization of formula (3), then make the polyalkylene oxide reaction of epihalohydrins and gained C-terminal carry out diepoxyization; Perhaps polyether glycol and the epihalohydrins reaction that obtains by the aklylene glycol molecule dehydrating condensation that makes aklylene glycol shown in the formula (4) or at least 2 carry out diepoxyization, thereby makes.
(in the formula, y R 2Identical or different, represent hydrogen atom or carbonatoms 1～6, preferred 1～2 alkyl, particularly R respectively 2Be hydrogen atom or methyl, x is 1～9, preferred 1～6 integer, and y is 1～50, preferred 1～20 integer)
(in the formula, R 2With x as described in the above-mentioned definition)
As the aklylene glycol of above-mentioned formula (4), for example can enumerate ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butyleneglycol, 1,3-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1, carbonatomss 2～10 such as 8-ethohexadiol, preferred 2～6 aklylene glycol.
The di-epoxy compounds (a11) of above-mentioned formula (1) and the di-epoxy compounds (a12) of formula (2) for example can be enumerated デ Na コ-Le EX-850 as commercially available product, デ Na コ-Le EX-821, デ Na コ-Le EX-830, デ Na コ-Le EX-841, デ Na コ-Le EX-861, デ Na コ-Le EX-941, デ Na コ-Le EX-920, (above be Na ガ セ ケ system テ Star Network ス Co., Ltd. system to デ Na コ-Le EX-931, trade(brand)name), グ リ シ エ-Le PP-300P, グ リ シ エ-Le BPP-350 (above Sanyo Chemical Industries, Ltd. system, trade(brand)name) etc.
Di-epoxy compounds (a1) can be distinguished and uses compound (a11) and compound (a12) separately or be used in combination both.
Resins, epoxy (a2):
The employed Resins, epoxy of manufacturing (a2) of modified epoxy (A1) is the compound that has at least 2 epoxy group(ing) in 1 molecule, can have number-average molecular weight in general 340～1500, preferred 340～1000 scopes and the epoxy equivalent (weight) in general 170～500, preferred 170～400 scopes.Resins, epoxy (a2) especially preferably obtains by the reaction of polyphenolic substance and epihalohydrins, for example Epicholorohydrin.
In this specification sheets, " number-average molecular weight " is following tries to achieve: the method for being put down in writing according to JIS K 0124-83, use 4 of " TSKgel G4000HXL ", " TSKgel G3000HXL ", " TSKgelG2500HXL " and " TSKgel G2000HXL " (above eastern ソ-Co., Ltd.'s system, trade(brand)names) as separator column, use GPC to use tetrahydrofuran (THF) as elutriant, under 40 ℃ and flow velocity 1.0ml/ minute, try to achieve by the color atlas that utilizes the RI refractometer to obtain and polystyrene standard typical curve.
As being used to make the polyphenolic substance that Resins, epoxy (a2) uses, for example can enumerate two (4-hydroxy phenyls)-2,2-propane [dihydroxyphenyl propane], two (4-hydroxy phenyl) methane [Bisphenol F], two (4-hydroxy-cyclohexyl) methane [A Hydrogenated Bisphenol A F], 2, two (4-hydroxy-cyclohexyl) propane [Hydrogenated Bisphenol A] of 2-, 4,4 '-dihydroxy benaophenonel, two (4-hydroxy phenyls)-1,1-ethane, two (4-hydroxy phenyls)-1, the 1-Trimethylmethane, two (4-hydroxyl-2 or 3-tert-butyl-phenyls)-2,2-propane, two (2 hydroxy naphthalene base) methane, four (4-hydroxy phenyls)-1,1,2,2-ethane, 4,4 '-dihydroxy-diphenyl sulfone, the phenol phenolic novolac, cresols phenolic novolac etc.
In addition, the Resins, epoxy that obtains of the reaction by polyphenolic substance and Epicholorohydrin is preferably by material shown in the dihydroxyphenyl propane deutero-formula (5).
Figure A200810213834D00091
(in the formula, n is 0～2)
As the commercially available product of this Resins, epoxy, for example can enumerate the material of selling with jER828EL, jER1001 trade(brand)name by japan epoxy resin (strain).
Bisphenol cpd (a3):
Bisphenol cpd (a3) comprises the compound shown in the general formula (6), can enumerate two (4-hydroxy phenyls)-2 particularly, 2-propane [dihydroxyphenyl propane], two (4-hydroxy phenyl) methane [Bisphenol F] etc.
Figure A200810213834D00101
(in the formula, R 5And R 6Represent the alkyl of hydrogen atom or carbonatoms 1～6 respectively, preferably represent the alkyl of hydrogen atom or carbonatoms 1～2, R 7, R 8, R 9, R 10, R 11, R 12, R 13And R 14Represent the alkyl of hydrogen atom or carbonatoms 1～6 respectively, preferably represent hydrogen atom)
Modified epoxy (A1):
Modified epoxy (A1) can followingly obtain usually: suitably in the presence of as the tertiary amine such as for example dimethyl benzylamine, tributylamine etc. of catalysts or quaternary ammonium salts such as tetraethylammonium bromide, Tetrabutyl amonium bromide etc., about 80～about 200 ℃, preferred about 90～made above-mentioned di-epoxy compounds (a1), Resins, epoxy (a2) and bisphenol cpd (a3) reaction under the about 180 ℃ temperature about 1～6 hour, preferred about 1～5 hour, thereby manufacturing.
In the above-mentioned reaction, for example can also use secondary amine such as diethylamine, dibutylamine, diethanolamine, dipropanolamine, Mono Methyl Ethanol Amine on a small quantity as catalysts, the epoxy reaction of these secondary amine and Resins, epoxy (a2) produces tertiary amine, and this tertiary amine works as catalysts.
When making modified epoxy (A1), di-epoxy compounds (a1), Resins, epoxy (a2) and bisphenol cpd (a3) can react in the following order: (i) their are reacted di-epoxy compounds (a1) and Resins, epoxy (a2) and the whole mixing of bisphenol cpd (a3); (ii) make di-epoxy compounds (a1) and bisphenol cpd (a3) reaction, then blending epoxy (a2) makes its reaction in this reactant of gained; (iii) make Resins, epoxy (a2) and bisphenol cpd (a3) reaction, then mixing di-epoxy compounds (a1) in the gained reactant makes its reaction.The carrying out situation and can follow the trail of of reaction according to the epoxy valency.
The usage ratio of di-epoxy compounds (a1), Resins, epoxy (a2) and bisphenol cpd (a3) is a benchmark with the solid state component total mass of di-epoxy compounds (a1) and Resins, epoxy (a2) and bisphenol cpd (a3), and di-epoxy compounds (a1) is generally 1～35 quality %, preferred 2～30 quality %, more preferably in the scope of 3～25 quality %; Resins, epoxy (a2) is generally 10～80 quality %, preferred 15～75 quality %, more preferably in the scope of 20～70 quality %; Bisphenol cpd (a3) is generally 10～60 quality %, preferred 15～50 quality %, more preferably in the scope of 17～47 quality %, even if reduce the volatile organic compounds in the cation electrodeposition coating thus, also can obtain the suitable property excellence of galvanic deposit coating on thickness retention and processibility and the alloy galvanized steel plate, the cation electrodeposition coating that non-corrosibility is good.
Above-mentioned reaction can suitably be carried out in solvent.Used solvent for example can be enumerated hydrocarbon systems such as toluene, dimethylbenzene, hexanaphthene, normal hexane; Esters such as methyl acetate, ethyl acetate, butylacetate system; Ketone such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone system; Acid amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE system; Alcohol such as methyl alcohol, ethanol, n-propyl alcohol, Virahol system; Aromatic series alkyl alcohols such as phenyl Trivalin SF, aminomethyl phenyl Trivalin SF; Ether alcohol such as ethylene glycol monobutyl ether, carbiphene based compound or their mixture etc.
So the modified epoxy (A1) that obtains generally can have 500～3000, the epoxy equivalent (weight) in preferred 600～2500, more preferably 600～2000 scopes.
Contain amino compound (A2):
Among the present invention, with modified epoxy (A1) reaction contain amino compound (A2) amino in modified epoxy (A1), introducing, be used for giving composition with the cationic of modified epoxy (A1) cationization, use contains and has at least 1 material with the amino of the active hydrogen of epoxy reaction.
As the amino compound (A2) that contains that uses with this purpose, for example can enumerate list or dialkylamines such as single methylamine, dimethylamine, mono aminoethane, diethylamine, single isopropylamine, diisopropylamine, monobutyl amine, dibutylamine; Monoethanolamine, diethanolamine, list (2-hydroxypropyl) amine, two (2-hydroxypropyl) amine, monomethyl monoethanolamine, alkanolamine such as single ethyl amido alcohol; The ketoimine thing of alkylene polyamines such as quadrol, propylene diamine, butanediamine, hexanediamine, tetren, penten, diethylamino propyl group amine, diethylenetriamine, Triethylenetetramine (TETA) and their polyamines; Alkylene imine such as ethylene imine, 2-methyl ethylene imine; Cyclic amine such as piperazine, morpholine, pyrazine etc. can also be used the amine with the primary amine ketoimineization.
The modified epoxy (A) that contains amino that uses in the cation electric deposition paint composition of the present invention can be made by making the above-mentioned modified epoxy of compound (A2) (A1) that contains amino carry out addition reaction.
Composition in the above-mentioned addition reaction (A1) and usage ratio (A2) there is no strict restriction, can be according to the appropriate changes such as purposes of electrodeposition coating composition of the present invention, the total solid state component quality that contains the amino used modified epoxy of modified epoxy (A) (A1) and contain the compound (A2) of amino with manufacturing is a benchmark, and modified epoxy (A1) is generally 65～95 quality %, is preferably 70～94 quality %, more preferably in the scope of 75～94 quality %; Contain amino compound (A2) be generally 5～35 quality %, be preferably 6～30 quality %, more preferably in the scope of 6～25 quality %.
Above-mentioned addition reaction usually can be in appropriate solvent carries out under about 80～about 170 ℃, preferred about 90～about 150 ℃ temperature about 1～6 hour, preferred about 1～5 hour.
The solvent of above-mentioned reaction for example can be enumerated hydrocarbon system compounds such as toluene, dimethylbenzene, hexanaphthene, normal hexane; Ester based compounds such as methyl acetate, ethyl acetate, butylacetate; Ketone based compounds such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone; Acid amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE based compound; Pure based compounds such as methyl alcohol, ethanol, n-propyl alcohol, Virahol; Aromatic series alkyl alcohols such as phenyl Trivalin SF, aminomethyl phenyl Trivalin SF; Ether alcohol such as ethylene glycol monobutyl ether, carbiphene based compound or their mixture etc.
The xylene formal dehyde resin modification contains amino Resins, epoxy (B):
The xylene formal dehyde resin modification contains amino Resins, epoxy (B) for reacting the resin that obtains by to make epoxy equivalent (weight) be 180～2500 Resins, epoxy (b1) with having the xylene formal dehyde resin (b2) of phenol hydroxyl and contain amino compound (b3).
Resins, epoxy (b1):
The xylene formal dehyde resin modification contains the viewpoints such as non-corrosibility of Resins, epoxy (b1) from filming of using as starting raw material in the manufacturing of amino Resins, epoxy (B), especially preferably the Resins, epoxy that obtains of the reaction by polyphenolic substance and epihalohydrins, for example Epicholorohydrin.
The polyphenolic substance that uses as being used to form this Resins, epoxy, for example can enumerate two (4-hydroxy phenyls)-2,2-propane [dihydroxyphenyl propane], two (4-hydroxy phenyl) methane [Bisphenol F], two (4-hydroxy-cyclohexyl) methane [A Hydrogenated Bisphenol A F], 2, two (4-hydroxy-cyclohexyl) propane [Hydrogenated Bisphenol A] of 2-, 4,4 '-dihydroxy benaophenonel, two (4-hydroxy phenyls)-1,1-ethane, two (4-hydroxy phenyls)-1, the 1-Trimethylmethane, two (4-hydroxyl-2 or 3-tert-butyl-phenyls)-2,2-propane, two (2 hydroxy naphthalene base) methane, four (4-hydroxy phenyls)-1,1,2,2-ethane, 4,4 '-dihydroxy-diphenyl sulfone, the phenol phenolic novolac, cresols phenolic novolac etc.
In addition, in the Resins, epoxy that obtains of the reaction by polyphenolic substance and Epicholorohydrin preferably by material shown in the following formula of dihydroxyphenyl propane deutero-(7).
Figure A200810213834D00121
(in the formula, n is 0～8, is preferably 1～7)
Resins, epoxy (b1) generally can have 180～2500, the epoxy equivalent (weight) in preferred 200～2000, more preferably 400～1500 scopes, in addition, preferably has 300, particularly 400～4000 at least, further is the number-average molecular weights in 800～2500 scopes.
Commercially available product as this Resins, epoxy.For example can enumerate the material of selling with trade(brand)names such as jER828EL, jER1002, jER1004, jER1007 by ジ ヤ パ Application エ Port キ シ レ ジ Application (strain).
Xylene formal dehyde resin (b2) with phenol hydroxyl:
Xylene formal dehyde resin (b2) have can with the phenol hydroxyl of epoxy reaction, be the composition that the plasticized (modification) to Resins, epoxy (b1) works.
This xylene formal dehyde resin (b2) with phenol hydroxyl for example can be made by make dimethylbenzene and formaldehyde, according to circumstances phenols generation condensation reaction in the presence of an acidic catalyst.Above-mentioned dimethylbenzene can use ortho-xylene ,-dimethylbenzene, right-dimethylbenzene or their mixture, in addition, can enumerate the compound etc. that the industrial formalin that can obtain easily, paraformaldehyde, trioxane etc. produce formaldehyde as above-mentioned formaldehyde.
And, above-mentioned phenols comprises 1 yuan or 2 yuan of phenoloids with 2 or 3 reaction site, specifically for example can enumerate phenol, cresols class (ortho-cresol, meta-cresol, p-cresol), paraoctyl phenol, nonylphenol, biphenol propane, biphenol methane, Resorcinol, pyrocatechol, quinhydrones, p-tert-butylphenol, bisphenol sulphone, bis-phenol ether, p-phenyl phenol etc., these materials may be used singly or in combin more than 2 kinds.Wherein, preferred especially phenol and cresols class.
The employed an acidic catalyst of above-mentioned condensation reaction for example can be enumerated sulfuric acid, hydrochloric acid, tosic acid, oxalic acid etc., general special preferably sulfuric acid.Its usage quantity is because the usually dilution of the water in formalin, thus the concentration in the aqueous solution can scope for 10～50 quality % in.
Condensation reaction for example can be by being heated to backflows such as the dimethylbenzene that exists in the reaction system, phenols, water, formaldehyde temperature, the temperature in about 80～about 100 ℃ of scopes is carried out usually, can make its end usually about 2～6 hours.
Under these conditions, by in the presence of an acidic catalyst, making dimethylbenzene and formaldehyde and phenols reacting by heating as required, can obtain xylene formal dehyde resin.In addition, xylene formal dehyde resin can also according to circumstances make the xylene formal dehyde resin and the phenols reaction of manufacturing in advance and obtain in the presence of an acidic catalyst.
So the xylene formal dehyde resin (b2) that obtains generally can have 20～50000mPas (25 ℃), preferred 25～30000mPas (25 ℃), the more preferably viscosity in 30～15000mPas (25 ℃) scope, and preferably have 100～50000, preferred especially 150～30000, the further phenol hydroxyl equivalent in preferred 200～10000 scopes.
Contain amino compound (b3):
Be at epoxy resin-base introducing amino, be used for giving composition with the amino compound (b3) that contains of Resins, epoxy (b1) reaction, can use the compound that contains amino equally of compound (A2) example of when manufacturing contains amino modified epoxy (A), using that contains amino the cationic of this cationic epoxy resinization.
The xylene formal dehyde resin modification of using as resinous principle in the cation electric deposition paint composition of the present invention contains amino Resins, epoxy (B) can be by utilizing itself known method to make xylene formal dehyde resin (b2) and containing amino compound (b3) and Resins, epoxy (b1) carries out addition reaction and makes.
Can carry out with random order with respect to the xylene formal dehyde resin (b2) of Resins, epoxy (b1) and the reaction that contains amino compound (b3), preferably make xylene formal dehyde resin (b2) simultaneously and contain amino compound (b3) and react with respect to Resins, epoxy (b1).
Above-mentioned addition reaction usually can be in appropriate solvent, about 80～about 170 ℃, preferred about 90～carry out under the about 150 ℃ temperature about 1～6 hour, preferred about 1～5 hour.The solvent of above-mentioned reaction for example can be enumerated hydrocarbon system compounds such as toluene, dimethylbenzene, hexanaphthene, normal hexane; Ester based compounds such as methyl acetate, ethyl acetate, butylacetate; Ketone based compounds such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone; Acid amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE based compound; Pure based compounds such as methyl alcohol, ethanol, n-propyl alcohol, Virahol; Aromatic series alkyl alcohols such as phenyl Trivalin SF, aminomethyl phenyl Trivalin SF; Ether alcohol such as ethylene glycol monobutyl ether, carbiphene based compound or their mixture etc.
The usage ratio of each reacted constituent of above-mentioned addition reaction there is no strict qualification, can be according to the present invention the appropriate changes such as purposes of electrodeposition coating composition, with Resins, epoxy (b1), xylene formal dehyde resin (b2) and total solid state component quality of containing amino compound (b3) 3 compositions is benchmark, in the preferred following scope.
Resins, epoxy (b1): be generally 50～90 quality %, be preferably 50～85 quality %, more preferably 53～83 quality %,
Xylene formal dehyde resin (b2): be generally 5～45 quality %, be preferably 6～43 quality %, more preferably 6～40 quality %,
Contain amino compound (b3): be generally 5～25 quality %, be preferably 6～20 quality %, 6～18 quality % more preferably.
Block polyisocyanate curing agent (C):
Above-described modified epoxy (A) and the xylene formal dehyde resin modification that contains amino contains amino Resins, epoxy (B) by being used in combination with block polyisocyanate curing agent (C), can prepare the cation electric deposition paint composition of Thermocurable.
Above-mentioned block polyisocyanate curing agent (C) is polyisocyanate compound and the agent of isocyanic ester block with the addition reaction product of chemical theory amount roughly.As the polyisocyanate compound that uses in the block polyisocyanate curing agent (C), can use itself compound known, for example can enumerate tolylene diisocyanate, Xylene Diisocyanate, phenylene vulcabond, ditan-2,2 '-vulcabond, ditan-2,4 '-vulcabond, ditan-4,4 '-vulcabond, thick MDI[polymethylene polyphenyl isocyanate], two (methyl isocyanate) hexanaphthene, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, aromatic series such as isophorone diisocyanate, aliphatics or alicyclic polyisocyanates compound; The cyclized polymer of these polyisocyanate compounds or biuret body; Perhaps their combination.
Viewpoint from non-corrosibility, preferred especially tolylene diisocyanate, Xylene Diisocyanate, phenylene vulcabond, ditan-2,4 '-vulcabond, ditan-4, aromatic polyisocyanate compounds such as 4 '-vulcabond, thick MDI.
On the other hand, embedding is carried out in above-mentioned isocyanic ester block agent addition on the isocyanate group of polyisocyanate compound disconnected, stable at normal temperatures by the blocked polyisocyanates compound that addition produces, preferably when being heated to the burn-back temperature of filming (about 100～about 200 ℃ usually), the block agent compound of free isocyanate group that dissociates, can regenerate.
The block agent of using in the block polyisocyanate curing agent (C) for example can be enumerated oxime compounds such as methyl ethyl ketoxime, cyclohexanone-oxime; Phenol system compounds such as phenol, p-tert-butylphenol, cresols; Aliphatics such as propyl carbinol, 2-Ethylhexyl Alcohol alcohols; Aromatic series alkanols such as phenyl Trivalin SF, aminomethyl phenyl Trivalin SF; Ether alcohol such as ethylene glycol monobutyl ether, carbiphene based compound; Lactan such as ε-Ji Neixianan, butyrolactam based compound etc.
Cation electric deposition paint composition:
The containing of cation electric deposition paint composition of the present invention stating composition (A), (B) and solid state component total mass (C) more than the cooperation ratio that amino modified epoxy (A), xylene formal dehyde resin modification contain amino Resins, epoxy (B) and block polyisocyanate curing agent (C) is benchmark, and composition (A) can be for 5～60 quality %, be preferably 8～50 quality %, 8～40 quality % more preferably; Composition (B) can be for 5～60 quality %, be preferably 10～55 quality %, 15～53 quality % more preferably; Composition (C) can be 10～40 quality %, be preferably 15～35 quality %, more preferably in the scope of 18～35 quality %, contain amino modified epoxy (A) by cooperating with these ratios, the xylene formal dehyde resin modification contains amino Resins, epoxy (B) and block polyisocyanate curing agent (C), paint stability is good, even and if the volatile organic compounds in the minimizing cation electrodeposition coating, also can obtain the thickness retention excellence, the suitable property excellence of galvanic deposit coating on processibility and the alloy galvanized steel plate, and the cation electric deposition paint composition of the non-corrosibility excellence of filming.
When preparing cation electric deposition paint composition of the present invention, usually at first contain and add various additives such as tensio-active agent, surface conditioner or organic solvent etc. as required in amino Resins, epoxy (B) and the block polyisocyanate curing agent (C) and mix fully containing amino modified epoxy (A), xylene formal dehyde resin modification, and then with organic carboxyl acid with resin (A) and/or (B) neutralization, carry out water-solubleization or water-dispersionization, obtain milk sap.Above-mentioned neutralization can be used itself known organic carboxyl acid, wherein preferred acetate, formic acid, lactic acid or their mixture.Then, in gained milk sap, add the colo(u)rant dispersion thickener, adjust resin solid component concentration or viscosity etc., can prepare cation electric deposition paint composition of the present invention by water.
Above-mentioned colo(u)rant dispersion thickener is for being dispersed with pigment class such as tinting pigment, rust-stabilising pigment, filler pigment in colo(u)rant dispersion in advance in resin with the minuteness particle shape, for example can be by colo(u)rant dispersion is disperseed in the mixing machines with for example pack into ball mill, pebble mill, pebble mill etc. of resin, neutralizing agent and pigment class, carry out dispersion treatment, thus preparation.
As above-mentioned colo(u)rant dispersion resin, can use itself known substances, for example have matrix resin, polymeric surface active agent, tertiary amine-type Resins, epoxy, quaternary Resins, epoxy, uncle's sulfonium salt type Resins, epoxy of hydroxyl and cationic group etc.Above-mentioned colo(u)rant dispersion is generally in the scope of 1～150 mass parts, preferred especially 10～100 mass parts with respect to pigment class and colo(u)rant dispersion total amount 100 mass parts with resin with the usage quantity of resin.
Above-mentioned pigment class is not particularly limited, and for example can enumerate painted pigment such as cooperating titanium oxide, carbon black, iron oxide red; Filler pigments such as clay, talcum, barium oxide, lime carbonate, silicon-dioxide; Molybdic acid aluminium, aluminium triphosphate, zinc oxide rust-stabilising pigments such as (zinc white).The use level of these pigment class is preferably 1～100 mass parts, preferred especially 5～75 mass parts usually, is more preferably in the scope of 10～50 mass parts with respect to composition (A), (B) and total solid state component 100 mass parts (C).
In addition, in the cation electric deposition paint composition of the present invention,, can cooperate bismuth compound for the corrosion that suppresses coated article or antirust.This bismuth compound for example can be enumerated bismuth oxide, bismuth hydroxide, alkaline carbonic acid bismuth, Bismuth trinitrate, bismuth silicate, organic acid bismuth (for example bismuth lactate) etc.
And, in the cation electric deposition paint composition of the present invention, in order to improve curing of coating, can cooperate organo-tin compounds such as dibenzoic acid dibutyl tin, di-n-octyltin oxide, dibutyltin oxide, by the above-mentioned zinc oxide of an amount of use rust-stabilising pigment and/or bismuth compounds such as (zinc white) and/or after miniaturization, use, under the situation of not using these organo-tin compounds, also can seek the raising of curing of coating.
Can also contain organic solvent in the cation electric deposition paint composition of the present invention.7.7 quality %), Virahol (water solubility: freely mix), 2-Ethylhexyl Alcohol (water solubility: 0.07), benzylalcohol (water solubility: 3.8 quality %), ethylene glycol (water solubility: freely mix), propylene glycol pure series solvents such as (water solubilities: freely mix) organic solvent that can use for example can be enumerated methyl alcohol (water solubility: freely mix), ethanol (water solubility: freely mix), propyl carbinol (water solubility:; Ethylene glycol monomethyl ether (water solubility: freely mix), glycol monomethyl butyl alcohol (water solubility: freely mix), ethylene glycol mono hexyl ether (solubleness in the water: 0.99 quality %), glycol monomethyl 2-ethylhexyl ether (water solubility: 0.09 quality %), diglycol monotertiary butyl ether (water solubility: freely mix), propylene glycol monomethyl ether (water solubility: freely mix), propylene glycol list phenyl ether (water solubility: insoluble), 3-methyl-3-methoxybutanol (water solubility: freely mix), carbiphene (water solubility: freely mix), diglycol monotertiary butyl ether ether series solvents such as (water solubilities: freely mix); 2.0 quality %), pimelinketone (water solubility: 5.0 quality %), isophorone (water solubility: 1.2 quality %), methyl ethyl diketone (water solubility: ketone series solvent such as 12.5 quality %) acetone (water solubility: freely mix), methyl iso-butyl ketone (MIBK) (water solubility:; 22.9 quality %), ethylene glycol monobutyl ether acetic ester (water solubility: ester series solvent or their mixture such as 0.9 quality %) ethylene glycol monomethyl ether acetate (water solubility:.
Even if the volatile organic compounds from reduce cation electric deposition paint composition, also can obtain the thickness retention excellence, and processibility, the viewpoint of the cation electric deposition paint composition of the suitable property excellence of galvanic deposit coating on the alloy galvanized steel plate is set out, in the cation electric deposition paint composition of the present invention, solubility parameter be 8～10 and water solubility be that the content of the above organic solvent (D) of 95 quality % is that benchmark is below the 1.0 quality % with the total mass of being bathed by the cation electrodeposition coating of cation electric deposition paint composition preparation of the present invention, be preferably below the 0.5 quality %, and the total amount of the organic solvent of bathing according to cation electrodeposition coating is below the 2.0 quality %, the following ratio of preferred 1.5 quality % contains organic solvent.
Above-mentioned organic solvent (D) for example can be enumerated ethylene glycol monobutyl ether, diglycol monotertiary butyl ether etc. particularly.
In addition, in order to reach minimizing (low VOCization), preferably with the milk sap desolventizing as the organic solvent amount of cation electric deposition paint composition purpose of the present invention.By carrying out desolventizing, the total mass of bathing with cation electrodeposition coating is a benchmark, solubility parameter be 8～10 and water solubility be that the content of the above organic solvent (D) of 95 quality % is that 1.0 quality % the total amount following and organic solvent that cation electrodeposition coating is bathed is below the 2.0 quality %.
Coating:
Cation electric deposition paint composition of the present invention so long as can then be not particularly limited in galvanic deposit, can be coated on arbitrarily on the coated article, coated article can be enumerated cold-rolled steel sheet, alloy galvanized steel plate, electrogalvanizing steel plate, electro-galvanizing-iron double-layer plate, organic compound steel plating plate, Al raw material, Mg raw material etc. particularly and these metal sheets be carried out carrying out metal foils such as surface treatment such as phosphate chemical conversion process, chromate treating after the surface washing processing such as alkali degreasing as required; Use the body of a motor car, bicycle assembly parts, domestic electric appliances, other machine of the processing of these metal foils etc.
Cation electric deposition paint composition can be coated on the required coated article surface by galvanic deposit.The cationic electrodeposition coating generally will reach in about 5～about 40 quality %, the preferred about 8～about 25 quality % scopes with dilutions such as deionized water, solid component concentration, and then the electrodeposition bath that electrodeposition coating composition of the present invention constitutes of comprising that pH is adjusted in 5.5～9.0, particularly 5.8～7.5 scopes is adjusted to and bathes about 15～about 35 ℃ of temperature, under the condition of load voltage 100～400V, preferred 150～380V, coated article is switched on as negative electrode, thereby carry out.After the galvanic deposit coating, unnecessary in order to remove attached to the cation electrodeposition coating on the coated article, use ultrafiltrated (UF filtrate), reverse osmosis permeate water (RO water), process water, pure water etc. to wash fully usually.
The thickness of electrodeposition coating is not particularly limited, generally based on cured coating film, and the scope of preferred 5～40 μ m, preferred especially 12～30 μ m.In addition, the burn-back of filming can followingly be carried out: for example use heat drying equipment such as electric hot air dryer, gas hot air dryer, heating electrodeposition coating about 10 minutes～180 minutes, preferred about 20 minutes～50 minutes under the temperature of about 110 ℃～about 200 ℃ of the temperature on coating thing surface, preferred about 140 ℃～about 180 ℃ and carry out, thus, electrodeposition coating is solidified, can obtain article with cation electric deposition paint composition coating of the present invention.
Embodiment
Below more specifically describe the present invention by Production Example, embodiment and comparative example, the present invention is not limited only to these." part " expression mass parts in each example, " % " expression quality %.
Contain the manufacturing of amino modified epoxy (A)
Production Example 1: the Production Example of matrix resin No.1
In the beaker of 2 liters of the internal volumes that has thermometer, reflux cooler and stirrer, put into 0.8 part of 950 parts of 185 parts of デ Na コ-Le EX-821 (annotate 1), jER828EL (annotating 4), 456 parts of dihydroxyphenyl propanes and Tetrabutyl amonium bromide, under 160 ℃, make its reaction, reach 800 until epoxy equivalent (weight).
Then, add 359 parts of methyl iso-butyl ketone (MIBK), 127 parts of the ketoimine things (purity 84%, methyl isobutyl ketone solution) that then add the methyl iso-butyl ketone (MIBK) of 150 parts of diethanolamine and diethylenetriamine, reacted 4 hours down at 120 ℃, obtain the matrix resin No.1 solution that contains amino modified epoxy of resin solid state component 80%.The amine value of matrix resin No.1 is that 69mgKOH/g and number-average molecular weight are 2400.
Production Example 2: the Production Example of matrix resin No.2
In the beaker of 2 liters of the internal volumes that has thermometer, reflux cooler and stirrer, put into 0.8 part of 950 parts of 471 parts of デ Na コ-Le EX-931 (annotate 2), jER828EL (annotating 4), 456 parts of dihydroxyphenyl propanes and Tetrabutyl amonium bromide, under 160 ℃, make its reaction, reach 950 until epoxy equivalent (weight).
Then, add 430 parts of methyl iso-butyl ketone (MIBK), 127 parts of the ketoimine things (purity 84%, methyl isobutyl ketone solution) that then add the methyl iso-butyl ketone (MIBK) of 150 parts of diethanolamine and diethylenetriamine, reacted 4 hours down at 120 ℃, obtain the matrix resin No.2 solution that contains amino modified epoxy of resin solid state component 80%.The amine value of matrix resin No.2 is that 60mgKOH/g and number-average molecular weight are 2500.
Production Example 3: the Production Example of matrix resin No.3
In the beaker of 2 liters of the internal volumes that has thermometer, reflux cooler and stirrer, put into 0.8 part of 950 parts of 340 parts of グ リ シ エ-Le BPP-350 (annotate 3), jER828EL (annotating 4), 456 parts of dihydroxyphenyl propanes and Tetrabutyl amonium bromide, under 160 ℃, make its reaction, reach 900 until epoxy equivalent (weight).
Then, add 400 parts of methyl iso-butyl ketone (MIBK), 127 parts of the ketoimine things (purity 84%, methyl isobutyl ketone solution) that then add the methyl iso-butyl ketone (MIBK) of 150 parts of diethanolamine and diethylenetriamine, reacted 4 hours down at 120 ℃, obtain the matrix resin No.3 solution that contains amino modified epoxy of resin solid state component 80%.The amine value of matrix resin No.3 is that 64mgKOH/g and number-average molecular weight are 2500.
Cooperation content and the parameter of the matrix resin No.1～No.3 of table 1 expression Production Example 1～3.
Figure A200810213834D00201
(annotating 1) デ Na コ-Le EX-821: Na ガ セ ケ system テ Star Network ス Co., Ltd. system, trade(brand)name, Resins, epoxy (di-epoxy compounds (a1)), epoxy equivalent (weight) 185.
(annotating 2) デ Na コ-Le EX-931: Na ガ セ ケ system テ Star Network ス Co., Ltd. system, trade(brand)name, Resins, epoxy (di-epoxy compounds (a1)), epoxy equivalent (weight) 471.
(annotating 3) グ リ シ エ-Le BPP-350: Sanyo changes into industrial society system, trade(brand)name, Resins, epoxy (di-epoxy compounds (a1)), epoxy equivalent (weight) 340.
(annotating 4) jER828EL: ジ ヤ パ Application エ Port キ シ レ ジ Application society system, trade(brand)name, Resins, epoxy (a2), epoxy equivalent (weight) 190, number-average molecular weight 380.
The xylene formal dehyde resin modification contains the manufacturing of amino modified epoxy (B)
Production Example 4: the manufacturing of xylene formal dehyde resin
In the divided beaker of 2 liters of the internal volumes that has thermometer, reflux cooler and stirrer, put into 424 parts of 480 parts of 50% formalin, 110 parts of phenol, 202 parts of 98% commercial sulphuric acids and m-xylenes, 84～88 ℃ of reactions 4 hours down.
Reaction is left standstill after finishing, after separation resin phase and the aqueous sulfuric acid phase, washed resin 3 times is mutually removed the unreacted Resorcinol 20 minutes under the condition of 20～30mmHg/120～130 ℃, obtain viscosity 1050mPas (25 ℃) through 480 parts of phenol-modified xylene formal dehyde resins.
Production Example 5: the Production Example of matrix resin No.4
In beaker, put into 0.2 part of 1140 parts of jER828EL (annotate 4), 456 parts of dihydroxyphenyl propanes and dimethyl benzylamine, under 130 ℃, make its reaction, reach 820 until epoxy equivalent (weight).
Then, add 420 parts of methyl iso-butyl ketone (MIBK), then add 300 parts of the xylene formal dehyde resins that Production Example 4 obtains, 127 parts of the ketoimine things (purity 84%, methyl isobutyl ketone solution) that then add the methyl iso-butyl ketone (MIBK) of 95 parts of diethanolamine and diethylenetriamine, reacted 4 hours down at 120 ℃, obtain the matrix resin No.4 solution that contains amino modified epoxy of resin solid state component 80%.The amine value of matrix resin No.4 is that 47mgKOH/g and number-average molecular weight are 2500.
The manufacturing of block polyisocyanate curing agent
Production Example 6: the Production Example of solidifying agent
In reaction vessel, add 127 parts of 270 parts of コ ス モ ネ-ト M-200 (trade(brand)name, Mitsui Chemicals society system, thick MDI) and methyl iso-butyl ketone (MIBK), be warming up to 70 ℃.To wherein the time with 1 hour drips 236 parts of ethylene glycol monobutyl ether, be warming up to 100 ℃ afterwards, Yi Bian keep this temperature, Yi Bian through time ground sampling, the absorption of using infrared absorption spectrum to measure the unreacted isocyanate group of affirmation disappears, and obtains the solidifying agent of resin solid state component 80%.
The manufacturing of milk sap
Production Example 7: the Production Example of milk sap No.1
37.5 parts in the solidifying agent (30 parts of solid state components) that mixes matrix resin No.4 that matrix resin No.1 12.5 parts of (10 parts of solid state components), Production Examples 5 that Production Example 1 obtains obtain 75 parts (60 parts of solid state components) and Production Example 6 acquisitions, and then add 13 parts of 10% acetate, after stirring equably, drip 156 parts of deionized waters with about 15 minutes time simultaneously intensely agitated, obtain milk sap.
Then, (below the 50mmHg) carries out remove (the so-called desolventizing) of organic solvent to gained milk sap under 35 ℃, decompression, and the content that makes the methyl iso-butyl ketone (MIBK) in the milk sap is below the 1 quality %.Then, in this milk sap, add 3 parts of ethylene glycol monobutyl ether, use deionized water to adjust solid state component, obtain the milk sap No.1 of solid state component 34%.
Production Example 8～23: the Production Example of milk sap No.2～No.17
Except the cooperation content of putting down in writing for table 2, similarly obtain milk sap No.2～No.17 with Production Example 7.
Production Example 24: the colo(u)rant dispersion Production Example of resin
In 1010 parts of jER828EL (with reference to annotating 4), add 0.2 part of 390 parts of dihydroxyphenyl propanes, 240 parts of プ ラ Network セ Le 212 (polycaprolactone glycol, ダ イ セ Le chemical industry Co., Ltd., trade(brand)name, weight-average molecular weight about 1250) and dimethyl benzylamine, 130 ℃ down reaction reach 1090 until epoxy equivalent (weight).
Then, add 150 parts of the lactic acid aqueous solutions of 134 parts of dimethylethanolamines and 90%, reacted 4 hours down at 120 ℃.Then add methyl iso-butyl ketone (MIBK) and adjust solid state component, obtain the colo(u)rant dispersion resin of the ammonium salt type resin system of solid state component 60%.Above-mentioned dispersion is 0.78mmol/g with the ammonium salt concentration of resin.
Production Example 25: the Production Example of colo(u)rant dispersion thickener No.1
Add 14.5 parts of titanium oxide in the colo(u)rant dispersion of the solid state component 60% that Production Example 24 obtains in resin 8.3 parts (5 parts of solid state components), make with extra care 7.0 parts of clays, 20.3 parts of 0.3 part of carbon black, 1 part of di-n-octyltin oxide, 1 part of bismuth hydroxide and deionized waters, use ball mill to disperse 20 hours, obtain the colo(u)rant dispersion thickener No.1 of solid state component 55%.
Production Example 26: the Production Example of colo(u)rant dispersion thickener No.2
Add 14.5 parts of titanium oxide in the colo(u)rant dispersion of the solid state component 60% that Production Example 24 obtains in resin 8.3 parts (5 parts of solid state components), make with extra care 6.0 parts of clays, 20.3 parts of 0.3 part of carbon black, 3.0 parts in zinc oxide and deionized waters, use ball mill to disperse 20 hours, obtain the colo(u)rant dispersion thickener No.2 of solid state component 55%.
The manufacturing of cation electrodeposition coating
Embodiment 1
In milk sap No.1 that Production Example 7 obtains 294 parts (100 parts of solid state components), add 297.6 parts of 55% colo(u)rant dispersion thickener No.1 that Production Example 20 obtains 52.4 parts (28.8 parts of solid state components) and deionized waters, the cation electrodeposition coating No.1 of acquisition solid state component 20%.
Embodiment 2～10
Similarly to Example 1, to cooperate content to make cation electrodeposition coating No.2～No.10 shown in the table 3.
Figure A200810213834D00251
Comparative example 1～8
Similarly to Example 1, to cooperate content to make cation electrodeposition coating No.11～No.18 shown in the table 4.
Figure A200810213834D00271
The making of test board
Each cation electrodeposition coating that uses embodiment and comparative example to obtain, to implement the cold-rolled steel sheet (0.8mm * 150mm * 70mm) or implemented the alloy galvanized steel plate that same chemical conversion handles (0.8mm * 150mm * of パ Le ボ Application De #3020 (Japanese パ-カ ラ イ ジ Application グ society system, trade(brand)name, zinc phosphate chemical conversion treating agent) 70mm) as coated article, carry out the galvanic deposit coating, make test board.For each test board of gained, carry out the coating performance test.It is the results are shown in following table 5 and table 6.
Figure A200810213834D00291
Figure A200810213834D00301
Organic solvent content during (annotating 6) bathes:
Gather each cation electrodeposition coating 10 μ l with micro-syringe, be injected into GC-15A (Shimadzu Seisakusho Ltd.'s system, trade(brand)name, gas-chromatography), measure under the following conditions.
Condition: post WAX-10 (ス ペ Le コ society system, trade(brand)name), column temperature are warming up to 200 ℃, carrier gas with 5 ℃/min and use He to measure.
The suitable property of galvanic deposit coating of (annotating 7) alloy galvanized steel plate:
To impregnated in electrocoating paint with the alloy galvanized steel plate that パ Le ボ Application De #3020 (Japanese パ-カ ラ イ ジ Application グ society system, trade(brand)name, zinc phosphate chemical conversion treating agent) carried out 0.8 * 150 * 70mm that chemical conversion handles and bathe (30 ℃) as negative electrode, carry out the galvanic deposit coating conduction time in the 210V adjustment, obtain the electrodeposition coating of 20 μ m thickness.For the test segment after it is solidified, calculate the pinhole number in 10cm * 10cm area, estimate according to following standard.
◎: can not produce pin hole
Zero: as seen produced 1 little pin hole, but be the hidden degree of filming in can using, no problem
△: produce 2～5 pin holes
*: produce 10 above pin holes
(annotating 8) non-corrosibility:
To impregnated in the cold-rolled steel sheet that パ Le ボ Application De #3020 (Japanese パ-カ ラ イ ジ Application グ society system, trade(brand)name, zinc phosphate chemical conversion treating agent) carried out 0.8 * 150 * 70mm that chemical conversion handles and carry out the galvanic deposit coating in each cation electrodeposition coating.Then, be to use hot air dryer 170 ℃ of following burn-backs 20 minutes, obtain to solidify the test board of thickness 20 μ m.
On filming, be carved into the feasible matrix that reaches test board of cross sliding injury with pocket knife, according to JISZ-2371 it is carried out 35 ℃ solvent spray test 840 hours, estimate according to following standard by the surface state (blister) that is coated with from rust, foaming scope and the general portion of cutting part.
◎: get rusty, blistered maximum range apart from (one-sided) below the 2.0mm of cut part,
Zero: get rusty, blistered maximum range apart from the cut part surpass 2.0 and (one-sided) below the 3.0mm,
△: get rusty, blistered maximum range apart from the cut part surpass 3.0mm and (one-sided) below the 3.5mm,
*: get rusty, blistered maximum range surpasses below the 3.5mm apart from the cut part.
(annotating 9) anti-exposure:
With the same condition of above-mentioned non-corrosibility under on each test board of making spraying coating WP-300 (coating in Northwest ペ イ Application ト Co., Ltd. system, trade(brand)name, the water-based) after solidifying thickness and reaching 25 μ m, utilize electric hot-air drier 140 ℃ of following burn-backs 30 minutes.And then, spraying coating ネ オ ア ミ ラ Star Network 6000 (Northwest ペ イ Application ト Co., Ltd. system, trade(brand)name, coatings) reach 35 μ m until solidifying thickness on filming in above-mentioned, utilize electric hot-air drier 140 ℃ of following burn-backs 30 minutes, make the exposure test coated plate.
Pocket knife carves the cross scar and makes and reach matrix on filming on the gained exposure test coated plate, after Chiba county thousand Cang Ding (seashore portion) flatly expose 1 year, estimates according to following standard by rust, foaming scope from knife wound.
◎: get rusty or blistered maximum range apart from the cut part one-sided less than 2mm,
Zero: get rusty or blistered maximum range apart from the cut part one-sided for more than the 2mm, less than below the 3mm,
△: get rusty or blistered maximum range apart from the cut part one-sided for more than the 3mm, less than below the 4mm,
*: get rusty or blistered maximum range one-sided for more than the 4mm apart from the cut part.
(annotating 10) processibility:
To impregnated in each cation electrodeposition coating with the cold-rolled steel sheet that パ Le ボ Application De #3020 (Japanese パ-カ ラ イ ジ Application グ society system, trade(brand)name, zinc phosphate chemical conversion treating agent) carried out 0.8 * 150 * 70mm that chemical conversion handles and carry out the galvanic deposit coating in bathing, acquisition is filmed, and utilizes hot air dryer to film 20 minutes at 170 ℃ of following burn-back gained.Utilize サ-Off テ ス ト 301 (ミ of Co., Ltd. Star ト ヨ society system, trade(brand)name, surface roughness measurement machine) to measure the surface roughness Ra value of the electrodeposition coating of gained test coated plate, estimate according to following standard.
Zero: Ra less than 0.25,
△: Ra is more than 0.25 and less than 0.35,
*: Ra surpasses 0.35.
(annotating 11) paint stability (water dispersible):
Under 30 ℃, container sealing was stirred each cation electrodeposition coating 30 days.Afterwards, use 400 order filtering nets to filter the cation electrodeposition coating total amount, measure residual volume (mg/L), according to following standard evaluation cation electrodeposition coating.
◎: the expression less than 5mg/L,
Zero: more than the expression 5mg/L and less than 10mg/L
△: expression 10mg/L above and less than 15mg/L,
*: more than the expression 15mg/L.
(annotating 12) thickness retention:
To impregnated in the cold-rolled steel sheet that パ Le ボ Application De #3020 (Japanese パ-カ ラ イ ジ Application グ society system, trade(brand)name, zinc phosphate chemical conversion treating agent) carried out 0.8 * 150 * 70mm that chemical conversion handles during each cation electrodeposition coating bathes, carry out 250V-3 minute galvanic deposit coating, measure the thickness (1) of filming.Then, stirred each cation electrodeposition coating 10 days at 30 ℃ of following open containers.Afterwards, other cold-rolled steel sheet be impregnated in each cation electrodeposition coating bath, carry out 250V-3 minute galvanic deposit coating, measure the thickness (2) of filming.
◎: the difference of thickness (1) and thickness (2) less than 1 μ m,
Zero: the difference of thickness (1) and thickness (2) be 1 μ m above and less than 4 μ m,
△: the difference of thickness (1) and thickness (2) be 4 μ m above and less than 7 μ m,
*: thickness (1) surpasses 7 μ m with the difference of thickness (2).
Industrial applicability
By cation electric deposition paint composition of the present invention, reduce cation even if can provide Volatility in the electrocoating paint, the electro-deposition coating adaptive on the alloy galvanized steel plate, anti-The coated article of corrosivity excellence.

Claims (13)

1. cation electric deposition paint composition is characterized in that it contains:
(A) contain amino modified epoxy, its following acquisition: making the di-epoxy compounds (a1), the epoxy equivalent (weight) that are selected from di-epoxy compounds (a12) shown in di-epoxy compounds (a11) shown in the general formula (1) and the general formula (2) is that 170～500 Resins, epoxy (a2) and bisphenol cpd (a3) reaction obtain modified epoxy (Al), make gained modified epoxy (Al) and contain amino compound (A2) reaction, thereby obtain;
Figure A200810213834C00021
In the formula, m or the individual R of n 1Identical or different, represent the alkyl of hydrogen atom or carbonatoms 1～6 respectively, m and n are respectively O or integer and m+n=1～20,
Figure A200810213834C00022
In the formula, y R 2Identical or different, represent the alkyl of hydrogen atom or carbonatoms 1～6 respectively, x is 1～9 integer, y is 1～50 integer,
(B) by to make epoxy equivalent (weight) be 180～2500 Resins, epoxy (b1) with have the xylene formal dehyde resin (b2) of phenol hydroxyl and contain the Resins, epoxy that xylene formal dehyde resin modification that amino compound (b3) reaction obtains contains amino; And
(C) block polyisocyanate curing agent,
With described composition (A), (B) and solid state component total mass (C) is benchmark, contains 5～60 quality % compositions (A), 5～60 mass parts % compositions (B) and 10～40 quality % compositions (C).
2. the described cation electric deposition paint composition of claim 1, in the formula (1), R 1Expression hydrogen atom or methyl.
3. the described cation electric deposition paint composition of claim 1, in the formula (2), R 2Expression hydrogen atom or methyl.
4. the described cation electric deposition paint composition of claim 1, wherein, Resins, epoxy (a2) has the number-average molecular weight in 340～1500 scopes.
5. the described cation electric deposition paint composition of claim 1, wherein, bisphenol cpd (a3) is selected from two (4-hydroxy phenyls)-2,2-propane and two (4-hydroxy phenyl) methane.
6. the described cation electric deposition paint composition of claim 1, wherein, solid state component total mass with diepoxy resin (a1), Resins, epoxy (a2) and bisphenol cpd (a3) is a benchmark, makes diepoxy resin (a1) 1～35 quality %, Resins, epoxy (a2) 10～80 quality % and bisphenol cpd (a3) 10～60 quality % reaction.
7. the described cation electric deposition paint composition of claim 1, wherein, with modified epoxy (A1), total solid state component quality of containing amino compound (A2) is benchmark, makes modified epoxy (A1) 65～95 quality % and contains amino compound (A2) 5～35 quality % reaction.
8. the described cation electric deposition paint composition of claim 1, wherein, Resins, epoxy (b1) has the number-average molecular weight in 400～4000 scopes.
9. the described cation electric deposition paint composition of claim 1, wherein, xylene formal dehyde resin (b2) has the viscosity in 20～50000mPas (25 ℃) scope.
10. the described cation electric deposition paint composition of claim 1, wherein, xylene formal dehyde resin (b2) has the phenol hydroxyl equivalent in 100～50000 scopes.
11. the described cation electric deposition paint composition of claim 1, wherein, with Resins, epoxy (b1), xylene formal dehyde resin (b2) and total solid state component quality of containing amino compound (b3) 3 compositions is benchmark, makes Resins, epoxy (b1) 50～90 quality %, xylene formaldehyde resin (b2) 5～45 quality % and contains amino compound (b3) 5～25 quality % reaction.
12. the described cation electric deposition paint composition of claim 1, wherein, with composition (A), (B) and solid state component total mass (C) is benchmark, contains composition (A) 8～50 quality %, composition (B) 10～55 quality % and composition (C) 15～35 quality %.
13. be coated with the article of each described cation electric deposition paint composition of claim 1～12.
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